Phosphite-imidazole catalyzed N-formylation and N-acylation of amines.

A novel and convenient method for the N-formylation reaction of amines with DMF as a formylating agent has been developed, utilizing a catalytic amount of diethyl phosphite/imidazole. Diethyl phosphite, as a nucleophilic catalyst, plays a significant role in this conversion. The presented method has a broad substrate scope, and various N-formyl products were obtained in good to excellent yields. Moreover, by using DMA instead of DMF, the N-acetylation reaction was also successful. The reaction of o-phenylenediamines with DMF afforded the corresponding benzimidazoles. Furthermore, N-sulfonyl amidines were obtained in good to excellent yields by the reaction of sulfonamides with DMF under similar conditions.

Hydroxy- and Amino-Phosphonates and -Bisphosphonates: Synthetic Methods and Their Biological Applications.

Phosphonates and bisphosphonates are stable analogs of phosphates and pyrophosphates that are characterized by one and two carbon-phosphorus bonds, respectively. Among the various phosphonates and bisphosphonates, hydroxy and amino substitutes are of interest as effective in medicinal and industrial chemistry. For example, hydroxy bisphosphonates have proven to be effective for the prevention of bone loss, especially in osteoporotic disease. On the other hand, different substitutions on the carbon atom connected to phosphorus have led to the synthesis of many different hydroxy- and amino-phosphonates and -bisphosphonates, each with its distinct physical, chemical, biological, therapeutic, and toxicological characteristics. Dialkyl or aryl esters of phosphonate and bisphosphonate compounds undergo the hydrolysis process readily and gave valuable materials with wide applications in pharmaceutical and agriculture. This review aims to demonstrate the ongoing preparation of various classes of hydroxy- and amino-phosphonates and -bisphosphonates. Furthermore, the current review summarizes and comprehensively describes articles on the biological applications of hydroxyl- and amino-phosphonates and -bisphosphonates from 2015 until today.

ZnCl2-mediated stereo- and chemoselective synthesis of vinylphosphonates.

A highly chemo- and stereoselective synthesis of diethyl (E)-2-(alkylidene)-2-phosphonoacetonitriles via the Knoevenagel condensation reaction of carbonyl compounds with diethyl cyanomethylphosphonate in the presence of zinc chloride has been achieved. By the presented method, various E-isomers of arylmethylidene phosphonates rather than Horner-Wadsworth-Emmons olefination products were obtained in good to excellent yields. Their E configurations were determined by X-ray diffraction and NMR analyses. In addition, DFT calculations provided insights into the chemo- and stereoselectivity of the reaction.

ZnCl2-Mediated Double Addition of Dialkylphosphite to Nitriles for the Synthesis of 1-Aminobisphosphonates.

In this study, the double addition of dialkylphosphite to nitriles in a ZnCl2/Et3N system is described. The reaction was conveniently and directly used for the synthesis of biologically important 1-aminobisphosphonates (ABPs) from nitriles. The one-pot synthesis of 1-aminobisphosphonates from aldehydes via the in situ generation of nitriles is also described.